Manufacturie of aromatic esters



Nov. 14, 1944. s, TRYoN ET AL 2,362,865

l MANUFACTURE OF AROMATIC ESTERS Filed July 18, 1941 2 sheets-sheet 1 5a er T1 on BY .Byledict Nov. 14, 1944.

s. TRYoN ET AL 2,362,865 MANUFACTURE OF AROMATIC ESTERS Filed Julyls, 1941 2 sheets-sheet 2 P/lewa/ "aranaze lNvENToRs Sager Tryon BY Wm 3. Benedict AT'TORN' Patented 1\`1..w'.`14,1944y SagerTryon, Elmhurst, and William S. Benedict,

P'New York,`N.`;Y.', assignorstto .Generali-Chemic'aly Company,` New Yor ofl New Yori;v i

k, N. Y., a corporation Applicatio'nJuIy-j18, 1941, vSerial* No. 402,964 y* I "Iihisinvention relates to themanufacture. of

' t aromatic esters of carboni'c acid. f-rom'phenols and phosgene. llt isparticularlyconcerned with theimanutacture of. diphenyl vcarbonatos, dcresyl lcarbonates, 'and dinaphthyl carbonatos.

, -131Fi01y t0-.the present invention ,theV classical method. :for the, preparation o f diphenyli car- Donate,I hasinvolved` the treatment of .an aquey ous .solution of ,an .alkali-metal .phenate `with phosgene ,-gas, described by Hentsche1..r ',The

"manufactures-of. diphenyl carbonate byl heatingv phenol with'` phosgene in-lafltube, describedby f lKemp. also hasbeen tried. but does notfglive as satisfactoryyields as vthe Hentschelfprocess.. A footnoteappendedto lI-Ientschels article in "the Journal. fuer Praktische Chexnieoommentedlthat ture of pheno1.and aluminum vchloride to .prioduce kohlensaures phenylthe meltingpoint. of

, Which,'.acoording to Richtenrwas'" 'C`.'. Y,Whatpever the productprepared .by Richter, it apparentlyl was not diphenylf' carbonate, `the. melting point ofyvhichA is between 7.8.2 and '78."4""'C.l and not 88 C. Richterfhimsel'f apparentlyconclude'd that hisearly Work either wasof no importance or ,did noty concern diphenyl carbonate for in'his r'Ireatise .on Organic Chemistry"(`1'1`th, German .Richter had previouslyded phosgene into. a mix; j

substantially higher yields thanether process and as compared with the Hentschelprocess'redice's'haridling andelimin'atesthe necessity for converting; yphenol to alkali-metal. phenatfej, tl'ius 'avoiding consumption'of caustic'soda. K

itspreferred aspects theinv'ention involvesl passingfphosgene'finto Contact with, af' phenol containing 'between 0.006` and v'0504' equivalent weight of aluminum or titanium for each phen'oxy radicalfweight present (including. that-.present as. phenols., phenates, andV :phenyl carbonate's) Wnilethefzphenol is maintained .at a'rtemperature between '150 and2504 C. 'By vthis processxirom 90%v tov 98%..ofthe vphenol .may be convertedrto the "corresponding di-aryl Acarbonate with .a':yield,

vbas edgon phosgene, lof about "80 to-90 'or betitelt.

The process of the invention may be conducted with various dilutions'fof phosgene; Thus' substantially 100%fphosgene may yloenemployeclo'r' mixturescontaining as low-'as";10% to 20%, :of phosgene and the balanoei pref erably nitrogen mayloefused.` 4Theprocessmay be conducted-continuously or batch-Wise. `Contactofthe phosgenewith the phenol may be effected by -bubedition, translated 'to the English by "DAibey he l.makes no. reference 'to this early work ,andljin his discussion "of' dip'henyl' carbonate cites only .the vKempf andfHentschei methods of; :treparation. y

kIn accordance y hasibeen ioundthatv excellent yie'lds'of a diaryl carbonate may be obtainedby 'subjectinga'phee no1; or mixture of (phenolsfc'orresponding 4'tothe desired ester lto 'intimat'eeontact with the phosgene in the presenceof not moreft-ha-n'olZ equivae lent 'Weight ,of `an amphoteric metal,I foreach' phenox-y radical; weight present, including that present as r phenols, phenates, and `phenyl' car- `yvith the present invention'A it bonates. Examples-ofiamphoteric'rnetals which catalyze the desired 'reaction are-aluminum, vtito"- nium, iron,`zinc', and tin. Y

The metal may be addedin the .form -ofzff'ree metal or a soluloleA salt vsuch'v as the hazlideor phenate. If the free metal Vor ahalide Ais employed-the metalorg salt under the conditions v of treatment 'is for thev most .part converted-.to

` phenolkor plienols present; Itis probablerthatian equilibrium mixture `of.' .the metal4 chloride; the phenol, and the phenate is formed, The'processhas theadvantagesuoverfthe Kempf andf'Hentschelprocessesizin .that'zitis capable of bling the phcsgenejthrough the compound ign liquid phase (either molten or v.dissolved iin an inert. solvent) Instead 'of bubblingthe lphosgene throughthe phenol, the phenol may-A be passed into contact With-'thev-phosgene inthe Iform of; a

nlm ,or spr-ay.

' particularly `desirable vmethodof conducting the .reaction .involves bring-ingphosgenef-containingfgas into contact vwith phenol -or,preferably. a mixture of phenol. and diphenyl carbonate .containing; the [requisite proportiontofA promoting agent; .at a:.temperature valoovelthe boiling -point ofphenol'at the pressureprevailingthereon, for example Aat a .temperature above 180 but below 250 C..at, atmospheric pressure, whereby .the phofsgene` may. be absorbeclata rapid rate inthe mixture evenl With relatively ,low concentrations of phenol, lto form Ia productfoffhigh diphenyl carbonatecontentl' The gaseous .product ofthis treatment, .comprising nnreacted phosgenelvapors of' pheno1hydrogen chloride, v and .inert gas,.-is thenpassed intointimater contact with a vphenol;*cliphenyl carbonate mixture .containing a suitable-proportion of promoting. agent at.,a substantially lower temperature, for example at aatemperature. between' v150" rvC..-a^nd.-.180v C. .for atmospheric pressure operations, whereby Ithe gaseous y mixture is cooled,` residual ,phosgene -is absorbed',v and, phenolI vapors;l are -condensedfor absorbed.. Thetwo steps ofv theprocessimayfbe conducted in.y separate vessels or in the vsame vessel. Thus a contact column wherein the phosgene is bubbled up through Ia. body of phenol and diphenyl carbonate may be used-a high temperature being maintained at the bottom of the column and a relatively lower temperature near the top-to accomplish the desired purpose.

As illustrative of the phenyl carbonates which may-be prepared in accordance with the present invention, the following are mentioned:

carbonate, from alpha- The process may be conducted at ordinary atmospheric pressure or at elevated pressures. In the case ofthe unsymmetrical esters the desired product may be associated with varying proportions of symmetrical esters of each of the phenols present. The desired products may Ibe separated lby fractional distillation or by fractional crystallization.

The practical application of the invention to the production of diphenyl carbonate is further illustrated below with reference to the accompanying drawings wherein Fig. 1 shows apparatus especially suitable for ybatch operations; and

Fig. 2 shows apparatus adapted for continuous operations.

With particular reference to Fig. 1 of the drawings, the numerals I and Ia designate twin reactor or absorber units. Each of these reactor units is a vertically elongated, tower-like vessel adapted to contain a batch of phenol. Reactors I and la are provided with heating jackets 2 and 2a for maintaining the phenol at suitable reaction temperature, suitable valve-controlled gas distributors 3 and 3a for introducing phosgene into ithe respective reactors, and valve-controlled outlet conduits 4 and 4a for withdrawing gas from the reactors. Conduits 4 and 4a are united to a common conduit 5 which is connected with gas distributors 3 and 3a by valve-controlled branches 6 and 6a, respectively. Reactors I and la have liquid inlet pipes 7 and Ia for introducing phenol and catalyst, and liquid outlet pipes 8 and 8a for withdrawing liquid reaction product. The reactors I and la may be constructed of glass, copper, or other suitable material.

From reactors I and Ia gas exhaust conduits 9 and da, each provided with its shut-off valve, lead to cooler I which may be a simple heat exchanger or waste heat boiler. Cooler I0 is connected by conduit II with a phenol trap I2 and phenol trap I2 is connected Iby conduit I3 with a gas distributor I4 located at the botto-m of an absorption vessel I5. Vessel I may be generally similar to reactors I and la but need not be equipped with heating means since the vessel is provided for absorption of hydrogen chloride, which may be effected at ordinary temperature. Vessel I5 is provided with a valve-controlled water inlet pipe I6 and a valve-controlled hydrochloric acid outlet pipe I'I. From the top of vessel I5 gas conduit i3 leads to ldistributor I9 located in the bottom of a second absorption unit 2,6 similar to unit I5.. Unit 20, which is provided for removing any last traces of phosgene gas and hydrogen chloride from the exit gases before exhausting them to the atmosphere, has a valve-controlled inlet pipe 2I at the top for an alkaline wash liquor such as caustic soda solution or lime solution or slurry and a valve-controlled outlet pipe 22 at the bottom for spent washliquor. Gas outlet conduit 243 at the top may lead to a suitable stack.

It is desirable for accurate temperature control that reactors I and Ia, and interconnecting conduits and pipes, if any, be insulated against heat loss. Reaction temperature control may be automatic or manual.

In the operation of the above apparatus for manufacture of diphenyl carbonate from phenol, molten phenol, to which has been added about 1% -by weight of ,anhydrous aluminum chloride, 1/s% of metallic aluminum, or 21/3% of aluminum phenate is introduced by means of inlet pipes 'I and 1a into reactors land Ia until each reactor is charged to about the level indicated in the drawings. Reactors I and Ia are operated alternately as unit #l and unit #2, respectively. Thus, at the beginning of operations the various valves may be set to provide for flow of phosgene gas progressively through distributor 3 into unit I, up through unit I, through conduits 4, 5 and 6a, and distributor 3a, into reactor la, up through this reactor and out at 9a to cooler I.

With heating jackets 2 and 2a operated to maintain a liquid temperature of and with phenol to which has been added 1% by weight of aluminum chloride, phosgene gas may be passed into the system as outlined above at an hourly rate corresponding to 45 volumes of gas, measured at standard temperature and pressure, per volume of* liquid inthe two reactors. At least at the beginning, the phosgene is absorbed primarily in reactor I, and reactor la serves to remove the minor proportion of the phosgene which passes outof Areactor I.

Any gas not absorbed in units I and Ia, and hydrogen chloride formed as a by-product of the reaction pass off to cooler I and the mixture is cooled in this cooler to about 30 C. or as low as practical. The cooled gas then passes to phenol trap I2 where any phenol entrained by the gases may be removed.

The substantially phenol-free hydrogen chloride gas, which 4may contain a small proportion of phosgene, passes into water in absorber I5 where phosgene reacts to form carbon dioxide and hydrochloric acid and hydrogen chloride is absorbed to form hydrochloric acid.

Any gas not absorbed in unit I5and any carbon dioxide generated therein pass through conduit IB and distributor I9 into alkaline solution in absorber 20 where traces of phosgene or hydrogen chloride may be reacted with sodium hydroxide or sodium carbonate to form salt solution. If sodium lhydroxide is used, carbon dioxide in the gas will be absorbed to form sodium carbonate.

The introduction of phosgene may be continued in the above manner until the charge in unit I lthis coil. The phosgenev gas and apertures 33 for passage of liquid and which are arranged to provide a more or less tortuous now of liquid from top to bottom while providing for repeated redistribution of gas in the form of fine bubbles.; `Within and near the bottom of the tower there is disposed a gas distributor 34 provided with a valve-controlled inlet pipe 35. At the bottom of the tower there is also provided a Valve-controlled liquid outlet pipe 36. Disposed somewhat below the center of the tower is a heating coil 31, which may .contain any suitable heating iluid such as diphenyl vapor, high pressure or superheated steam, etc. At the top of the tower is a Valve-controlled phenol inlet pipe 38 and a gas outlet vconduit 39. More or less, as a safety measure the tower may be provided with a'heating pipe 40 having a valve 4I. This heating pipe may serve to heat the entire length of the tower to prevent solidification of materials within the tower or to remelt such materials in the event the tower should accidentally become cooled while it is charged.

Conduit 39 leads to the bottom of a second tower 42, which is divided into two sections. Each section of tower 42 maybe packed or may be merely a free space scrubber. i

The lower section of tower 42 is provided with a liquidl outlet pipey 43 at the bottom thereof, and a distributor 44 and supply pipe 45 at an intermediate point for spraying or otherwise introducing a suitable solvent. p

Disposed with and near the top of the upper section of tower 42, which may be similar to the lower section, there is a distributor 46 having a valve-controlled wash-Water inlet pipe 41. At the bottom of this section there is a wash product outlet pipe 48. From the top of tower 42 a gas conduit 49 may lead to a stack or a suitable alkali Washer for removing any traces of unreacted constituents.

In the operation of this apparatus `for the conversion of phenol to diphenylV carbonate by means of a gas comprising 25% phosgene and 75% nitrogen, phenol, to which has been added about 0.007 atom of aluminum metal or 0.005 mol of titanium tetrachloride per mol of phenol, is introduced at inlet 38 at a temperature of about 50 C. and at a rate regulated to maintain the tower substantially full of liquid up to the indicated liquid level. The body of phenol surrounding heating coil 31 is maintained at a temperature of around 200 to 230 C. by means of is introduced through distributor 34. |The gas contacts with hot reaction product comprising 90% to 98% diphenyl carbonate and is thereby heated to reaction temperature. Conversely, by this contact with the cool entering gas, the product may be cooled to a temperature around 100 C.; that is, to a relatively low temperature safely above the freezing point of the product. The product passes out through outlet 36 continuously at such a rate that it contains no t more than a few percent of residual phenol.

Employing aluminum phenate in a proportion of about 0.008 mol of aluminum phenate for each mol of phenol conversions between 95% and 100% of the phenol and between 95% and 98% of the phosgene to diphenyl carbonate have been obtained.

The diphenyl carbonate product from this process may be puriiied in the same manner as the product of the previous examples and aluminum phenate may be recoveredfor reuse in a asc'ases provided with small holes32 for passage of gas similar manner. The crude product may be used directly without any purification treatment, for themanufacture of the o-phenoxy benzoic acid phenyl ester as previously described.

'The reaction of phosgene with phenol occurs mainly in that' section of the apparatus in the vicinity of heater 31. The iiow of hot liquid down through this heater serves to spread out the high temperature zone below the heater and the passage of gas up from the heater serves to distribute the high temperature zone in an upward direction. In the reaction zone phenol is converted to diphenyl carbonate and the phosgene gas is progressively absorbed to provide a gas of progressively lower phosgene content. Heat exchange of the' hot gas with the cooler ingoing phenol serves to transfer heat-from the gas to the phenol and thus cool the gas while heating the phenol toward reaction temperature.

Hydrogen chloride and introgen, which may be cooled in tower 30 to a temperature approaching that of the entering molten phenol, say about 60 C., `are withdrawn from tower 30 and passed through conduit 39 to the lower section of tower 42 where they are'scrubbed and cooled to about 30 C. by a suitable solvent for phosgene and phenol, for example, benzene. The solution of phosgene and phenol in benzene may be withdrawn through outlet 43. From the lower section the cooled product gas, from which phosgene and phenol have been removed, enters the washing tower 42 where hydrogen chloride is removed by contact of the solution with an aqueous scrubbing agent, preferably water, to provide a hydrochloric acid product. Since phosgene, phenol, and other impurities may be eifectively removed in the lower section of this tower 42, a hydrochloric acid possessing a high degree of purity may be recovered directly from the upper scrubbing section provided this section is constructed of materials which are not attacked by hydrochloric acid and a water of good purity is used as absorbent.

AThe following examples illustrate the results that have been secured by the process of the present invention.

Example 1 39 C. melting point phenol, to which had been added 1% by weight of aluminum chloride (about 0,02 equivalent weight of aluminum per phenoxy radical weight), was gassed with phosgene at atemperature varying between the limits and 192 C. for 11/2 hours at a rate Iof about 1A; mol of phosgene per mol of phenol per hour, corresponding to a space velocity of 82. The product of this treatment comprised a crude diphenyl carbonate containing 91.21% diphenyl carbonate and had a setting point of 72 C. Upon distillation a distilled diphenyl carbonate of 78 C. melting point was obtained.- The yield of diphenyl carbonate based on phenol consumed was more than 98% of theoretical and based onv phosgene consumed about 79% of theoretical.

Example 2 Ortho-cresol distilling at to 191 C., to which had been added 1% by weight of aluminum chloride, Was gassed with 100% phosgene at a temperature varying between the limits 168 and C. for 1.8 hours at a rate of about 1A; `mol of phosgene per mol of cresol per hour, corresponding. to a space velocity of 72. The product of this treatment comprised a crude dicresyl carbonate containing 90.3% dicresyl carbonate rfelsbondingftd estese' vlpiy uct of this treatment, comprisedfcrude dicresyly of.dicresyl.carbonate-based andi a* 's cr'e'syl' "'arbonate based .on o-cresolcons'umed' was about 95% of theoretialland'basedpn'phosgene @wing-fd 211001.19001 Olf iireriial- 'Example 3... Meta-eres@ distnnng at zoz'fto 20.3 c., to which had been added 1%y Abyfit'eight'of. aluminumchloride, wasA gassed withv 100% phosgene at a temperature Varying between the 'limits y155 and. 196 C. 'for y1% hoursfat au, rate of about 1/3 molof phosgene per molof c'resol per hour, corresponding. in? asma-:venait f 'I4-1 The Prodcarbonatefcontaining 90.6%[dim-resyl carboti A atior'radifstilled di-m-cr'esyl carbonateof about 47.6 C.` meltingpointy wasobtained. The yield of dicresyl carbonate 'based onv'm-cresol consumed. was about on `phosgene consumed. about. 80% of theoretical.

` y Eample 4..

, kEacample 551;;

Beta-naphthol dissolved in) 1,1/5 times its weight of, aluminum hleide (based "im" beta# naphthol) wasadded. "ThemiXture-washeatd to 18o? to' 19o? c. and gassedjtg'nn'roca-prinsgene at a. space Velocity of 37, The di-2-naphtl'iylcarbonateproductwas recrystallzed from 'with ether.' The yield or toluene 'and washed di-2 -naphthyl carbonate basedo'n naphtholon- Suited was 'aan 65%.; .of neef-:Lucia ad 'based on phosgene cons ,ur'nedv about 74'%fo ftheoreti'al`. .It is. 'i0' ble 'uriersfvd' the' 'ampheteie 'rfiei `stated to be present inf' the'reaoton 'mixture usually present in the'fform `of"a com'- PUn'd.. theret. a' the' planete and/Q1. the' Chloride- Hoyer/,Cram Simplify the desc bien and@ provideawmmoab particular metal' present or the form in which it occurs,.the"airiourlt"o fA amphoteric metal cornpound 'present in the reaction mixture has been expressed throughout the specification and claims in terms of the free metaLvexcept in those `instances in which it is stated the reaction mixture contains. a denite amount of a specified amphoteric metal compound. Accordingly, reference in the accompanying claims to the reaction mixture as containing a specified amount of'am'photeric metal'does not 'necessarily mean that the metal is present in the reaction mX- ture in free metallic form.

We claim:

uct. of this treatment comprisedf a'jc'rud'e dicresyl.

nateandhad a'sett'ing, point of 45 C.' Upon dis- 19,2%` of theoretical and based` tained in the reaction; 'massjregardless f the @amg peint or, 49? c. Upon disti1--,

alyl' cabor'iate,`which comprises reacting phos-y e'ne witn'at least one iphenoi containingj as a promoting agent an amphoteric metal phenate` in'an amount corresponding to not more than 0.2\equiyale nt Wght of themetal per' v'phenoxy C., to`

ragial'weisht present," o 2:' The4V process for the manuiacture of .a diwhichcomprises Contacting gasefainiegasa prometieg'egsat afl am: letal. phenate. man' amount. corre.-

wnttal, perl enemy radial. Weight arrasa fer the-aangename' a diaryl. carbonate, which comprises reacting.. `phosg'en'e with `at'least'one phenohcontainingj'as. a

pomotna agent. aluminum.. phenate in .fan

214110111111.' @beginneling tof nbtyrorejthangf 0.2.

Int1 weight of. aiuminunij per. prie-noisy` .Weight present.

process for the. manufacture. of. a. diarylL carbonate, 'w 'ch comprises freactingphosewith at least one. phenol containingas a. ,.l'laari-i'amoil ding' tofnot more"thanl 0.2,v equiyalent ight.' Qi 'titl-intim pe'r phenoxy radical'weght.

pie nt.

5l process for;V thelmanilfactureffofi' aldi-I:

aryl. carb nate, 'whichK comprises'A contacting gas.-

, eo'us, 'hosgenewithfa' phenol inliquidphas at 'a tot entrate taining as vetween 150 C. and,'2502,"C. con;-

aildj. ofaqulr .Entwarnunt await. phenoky'ra'dical weight. present'. Y

6. TheV processfcr the manufacture of a di-aryl carbonate, which comprises contacting gaseous phosgene with a phenol in liquidphase at a temperature' between 150 C. and '250 C. containing a promoting agent titanium phenate in an amountc'orresponding' to between 0.006 and 0.04

quivalent' 'weight of titanium' per phenoxy radica'l'weight present.

l'7. The process for the manufacture of diphenyl l carbonate, which comprises intimately contactin g gaseous. pho'sgen'e with phenol at a temperature 'between 150 C. andr 250 C.Y containing. as

. .a promoting agent an amphoteric metal phenate an amount corresponding to' not'more'than 0.2 equivalent weight of amphoteric metal per y phenoxy radical weightv present.

carbonate, which comprises intimately contacting 'gaseousphosgene with phenol` in liquid phase at' atemperature between 150 C'. and 250 CL containing as' a promoting 'agent aluminum plfle'nate` in an' amount corresponding to not more than 0.2 equivalent weight ofy aluminumA `per pheoxy radial weight present- @arbonatawhch comprises 'intimately @Quia-'Cime gaseous phosgne with' phenol in' liquid phase ata temperature between 150' C.'and 250" C. and' containing as a'promoting agent titanium phenate in an amount corresponding to not more than 0.2

, equivalent weight of titanium per phenoxy radical weight present.

10. In the process for the manufacture of a di-aryl carbonate by reactingaphenol and phosgene, the improvement which comprises bringing the phosgene gas in'to contact with a molten mixture of the di-aryl carbonate and the correspondt more, than Gia.' quivalent weight,

'a' pldmiieg @sent aluminum phenaie.- z inan. amount, correpfmding. to

` 8. Ther process for the manufacture'of diph'enyl for' the'maniifature, of 'dipnenyi into contact with additional phenol diphenyl carbonate mixture maintained at a temperature below the boiling point of phenol at the pressure prevailing thereon so as to remove phenol from said gas.

12. In the process for the manufacture of diphenyl carbonate by reacting phenol and phosgene, the improvement which comprises bringing phosgene gas into contact with a reaction mixture of phenol and diphenyl carbonate containing aluminum. phenate corresponding to between 0.006 and 0.04 equivalentweight of aluminum per phenoxy radical weight' present, maintained at a temperature above the boiling point of phenol at the prevailing pressure and below the boiling point of diphenyl carbonate at said pressure, and

passing the resulting gas into contact with additional phenol diphenyl carbonate mixture containing aluminum phenate corresponding to bediphenyl carbonate mixture containing aluminum phenate corresponding to between 0.006 and 0.04 equivalent weight of aluminum per phenoxy radical weight present, maintained at a temperature between 150 and 180 C. so as to remove tween 0.006 and 0.04 equivalent weight of alnmil num per phenoxy radical weight present, maintained at a temperature below the boiling point of phenol at the pressure prevailing thereon so as to remove phenol from said gas.

13. In the process for the manufacture of diphenyl carbonate by reacting phenol and phosgene, the improvement which comprises bringing phosgene gas intocontact with a reaction mixture of phenol and diphenyl carbonate containing titanium phenate corresponding to between 0.006 and 0.04 equivalent weight of titanium per phenoxy radical weight present, maintained at a temperature above the boiling point of l phenol at the prevailing pressure and below the boiling point of diphenyl carbonate at said pressure', and passing the resulting gas into contact with/additional phenol diphenyl carbonate mixture containing titanium phenate corresponding tobetween 0.006 and 0.04 equivalent weight of titanium per phenoxy radical weight present,.m'aintained at a temperature below the boiling point of phenol at the pressure prevailing thereon so as to remove phenol from said gas.

14. The process. for the manufacture of diphenyl carbonate by reacting phenol andphosgene, which comprises bringing phosgene gas into intimate contact with a reaction mixture'I of phenol and diphenyl carbonate containinglalum'- inum phenate correspondingl to between 0.006

and 0.04 equivalent weight of aluminum per phenol from said gas.

l5. The process for the manufacture of diphenyl carbonate by reacting phenol and phosgene, whichcomprises bringing phosgene gas into intimate contact with a reaction mixture of phenol and diphenyl carbonate containing titanium phenatecorresponding to between 0.006 and 0.04 equivalent weight of titanium per phen'oxy radical Weight present, maintained at about atmospheric pressure and at a temperature between 180 and 250 C., and passing the resulting gas into contact with additional phenol diphenyl carbonate mixture containing titanium phenate corresponding to between 0.006 and 0.04 equivalent weight of titanium per phenoxy radical weight present, maintained at a temperature between and 180 C. so as to remove phenol from said gas.

16. The process for the manufacture of a diaryl carbonate, which comprises bringing phosgene into intimate contact with a solution of a phenol in an inert solvent maintained at a reaction temperature between 150 C. and 250 C. and containing as a promoting agent the phenate of an amphoteric metal with said phenol, in an amount corresponding to not more than 0.2 equivalent weight of amphoteric metal per phenoxy radical weight present.

1'7. `The process for the manufacture of a dinaphthyl carbonate, which .comprises bringing phosgene into intimate contact with a solution of a naphthol in an inert solvent maintained at a reaction temperature between 150 C. and 250 C. and containing as a promoting agent the naphtholate of an amphoteric metal with said naphthol, in an amount corresponding to not more than 0.2,equivalent-weight of amphoterio metal per naphthoxy radical weight present.

18. In the process for the manufacture of a diaryl carbonate, which comprises reacting a phenol with phosgene, the improvement which comprises bringing phosgene gas into Contact with a reaction mixture of a phenol and a diaryl carbonate corresponding thereto maintained at a temperature above the boiling point of the phenol at the prevailing pressure and below the boiling point of the carbonate at said pressure. and passing the resulting gas into contact with additional phenol-diaryl carbonate mixture maintained at a pressure below the boiling point of the phenol at the pressure prevailing thereon so as to remove the phenol from said gas.

' SAGER. TRYON.

WILLIAM S. BENEDICT. 

